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Issue 10, 2011
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Time-resolved velocity map imaging of methyl elimination from photoexcited anisole

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Abstract

To date, H-atom elimination from heteroaromatic molecules following UV excitation has been extensively studied, with the focus on key biological molecules such as chromophores of DNA bases and amino acids. Extending these studies to look at elimination of other non-hydride photoproducts is essential in creating a more complete picture of the photochemistry of these biomolecules in the gas-phase. To this effect, CH3 elimination in anisole has been studied using time-resolved velocity map imaging (TR-VMI) for the first time, providing both time and energy information on the dynamics following photoexcitation at 200 nm. The extra dimension of energy afforded by these measurements has enabled us to address the role of πσ* states in the excited state dynamics of anisole as compared to the hydride counterpart (phenol), providing strong evidence to suggest that only CH3 fragments eliminated with high kinetic energy are due to direct dissociation involving a 1πσ* state. These measurements also suggest that indirect mechanisms such as statistical unimolecular decay could be contributing to the dynamics at much longer times.

Graphical abstract: Time-resolved velocity map imaging of methyl elimination from photoexcited anisole

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Publication details

The article was received on 05 Nov 2010, accepted on 04 Jan 2011 and first published on 24 Jan 2011


Article type: Paper
DOI: 10.1039/C0CP02429E
Phys. Chem. Chem. Phys., 2011,13, 4494-4499

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    Time-resolved velocity map imaging of methyl elimination from photoexcited anisole

    D. J. Hadden, C. A. Williams, G. M. Roberts and V. G. Stavros, Phys. Chem. Chem. Phys., 2011, 13, 4494
    DOI: 10.1039/C0CP02429E

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